Patent GB-991142-A (GB)
Title: Improvements relating to new substituted 2-(2-hydroxyphenyl)-benztriazole compounds and their use
IPC: C08K5/3475
Filed: 1962-06-15
Abstract: The invention comprises substituted 2-(21-hydroxy - phenyl) - benztriazoles of the general formula <FORM:0991142/C2/1> wherein R1 represents hydrogen or an alkyl, alkenyl, cycloalkyl or aralkyl radical which are possibly substituted by carboxyl or carboxylic acid ester groups and R1 and "Acyl," together with the amino-nitrogen atom, can form a ring when R1 is a carbonyl or unsubstituted or alkyl-substituted methylene group, and wherein the nucleus may be substituted at the 4,5 or 6 positions by alkyl, alkoxy, carboxy, carboxylic acid ester or amide, sulphonic acid amide and alkylsulphonyl groups or halogen and at the 41 and 51 positions by alkyl, cycloalkyl, aralkyl and aryl groups, alkoxy groups or halogens. The "Acyl" group is a radical of the formula <FORM:0991142/C2/2> wherein X is a carbon atom or the radical <FORM:0991142/C2/3> and Y is oxygen, an imino group which with X and R2 forms a s-triazine or pyrimidine ring or, when X is carbon, a sulphur atom, and R2 is an alkenyl, cycloalkyl, aralkyl or substituted or unsubstituted alkyl or aryl group, or if X is carbon, R2 is hydrogen or an alkenyloxy, cycloalkyloxy or substituted or unsubstituted alkoxy, aryloxy or aralkyloxy group, or a substituted or unsubstituted amino group, an imino group of a saturated monocyclic heterocycle or if R1 and R2 are linked together, together with X and R1, R2 represents the remainder of a lactam or dioxopyrrolidine ring.  These compounds may be prepared by heating a 2(21-hydroxyphenyl) benztriazole compound having an acylatable amino group in the 31 position with an acylating agent, said amino compound being prepared by reducing a 2 - nitro - 21 - hydroxy - 31 - acylamino - 1,11 - azobenzene compound (see Division C4) and saponifying the 2(21-hydroxy-31-acylaminophenyl) benztriazole compound so formed or by nitration of a 51-substituted 2(21-hydroxyphenyl) benztriazole and reduction of the 31 nitro compound so formed.  Other methods for preparing the compounds of the invention are:  (1) reduction of a 2-nitro-21-hydroxy - 31 - acylamino - 1,11 - azobenzene; (2) oxidation of a 2 - amino - 21 - hydroxy-31 - acylamino - 1,11 - azobenzene; (3) oxidation of a 2-amino-21-alkoxy, or acyloxy, -31-acylamino - 1,11 - azobenzene to form 2(21-alkoxy, or acyloxy, - 31 - acylaminophenyl) benztriazole and subsequent dealkylation, or saponification; and (4) modification of existing groups in compounds of Formula I.  An intermediate of the formula <FORM:0991142/C2/4> may be isolated by the reduction of 2-nitro-21-hy droxy - 31 - acylamino - 1,11 - azobenzene with hydrosulphite and may be converted into the desired triazole by catalytic or zinc dust reduction.  Several examples of the preparation and use of the compounds of the invention are given (see Divisions B2, B5, C3, C4 and G2).  Reference has been directed by the Comptroller to Specification 878,362.ALSO:Synthetic and natural polymers are stabilized against light by the incorporation, usually as 0.001 to 5% by weight, therein of a compound of the general formula <FORM:0991142/C3/1> wherein R1 represents hydrogen or an alkyl, alkenyl, cycloalkyl or aralkyl radical which are possibly substituted by carboxyl or carboxylic acid ester groups and R1 and "Acyl," together with the amino-nitrogen atom, can form a ring when R1 is a carbonyl or unsubstituted or alkyl-substituted methylene group, and wherein the nucleus may be substituted at the 4, 5 or 6 positions by alkyl, alkoxy, carboxy, carboxylic acid ester or amide, sulphonic acid amide and alkylsulphonyl groups or halogen and at the 41 and 51 positions by alkyl, cyclo-alkyl, aralkyl and aryl groups, alkoxy groups or halogens. The "Acyl" group is a radical of the formula <FORM:0991142/C3/2> wherein X is a carbon atom or the radical <FORM:0991142/C3/3> and Y is oxygen, an imino group which with X and R2 forms a s-triazine or pyrimidine ring or, when X is carbon, a sulphur atom, and R2 is an alkenyl, cyclo-alkyl, aralkyl or substituted or unsubstituted alkyl or aryl group or, if X is carbon, R2 is hydrogen or an alkenyloxy, cyclo-alkyloxy or substituted or unsubstituted alkoxy, aryloxy or aralkyloxy group, or a substituted or unsubstituted amino group, an imino group of a saturated monocyclic heterocycle or if R1 and R2 are linked together, together with X and R1, R2 represents the remainder of a lactam or dioxopyrrolidine ring.  Specified polymers are the polymers and copolymers of ethylenically unsaturated monomers, polyacrylic compounds, polyesters, polyamides, polyester resins, cellulose, cellulose esters and ethers, and proteins.  Reference has been directed by the Comptroller to Specification 878,362.ALSO:Lacquers used to protect light-sensitive materials from light contain at least one compound of the general formula <FORM:0991142/C4-C5/1> wherein R1 represents hydrogen or an alkyl, alkenyl, cycloalkyl or aralkyl radical which are possibly substituted by carboxyl or carboxylic acid ester groups and R1 and "Acyl," together with the amino-nitrogen atom, can form a ring when R1 is a carbonyl or unsubstituted or alkyl-substituted methylene group, and wherein the nucleus may be substituted at the 4, 5 or 6 positions by alkyl, alkoxy, carboxy, carboxylic acid ester or amide, sulphonic acid amide and alkylsulphonyl groups or halogen and at the 41 and 51 positions by alkyl, cyclo-alkyl, aralkyl and aryl groups, alkoxy groups or halogens. The "Acyl" group is a radical of the formula <FORM:0991142/C4-C5/2> wherein X is a carbon atom or the radical <PICT:0991142/C4-C5/1> and Y is oxygen, an imino group which with X, and R2 forms a s-triazine or pyrimidine ring or, when X is carbon, a sulphur atom, and R2 is an alkenyl, cyclo-alkyl, aralkyl or substituted or unsubstituted alkyl or aryl group or, if X is carbon, R2 is hydrogen or an alkenyloxy, cycloalkyloxy or substituted or unsubstituted alkoxy, aryloxy or aralkyloxy group, or a substituted or unsubstituted amino group, an imino group of a saturated monocyclic heterocycle or if R1 and R2 are linked together, together with X and R1, R2 represents the remainder of a lactam or dioxopyrrolidine ring. Intermediates in some of the methods of preparation of compounds of Formula I are azo-dyes, e.g. those produced by diazo-coupling of (a) o-nitro-anilines with phenols, (b) o-nitro-anilines with acylaminophenols, or (c) 2-acyloxy-3-acyl-amino-anilines with an aminobenzene compound with subsequent hydrolysis of the acyloxy group.  A number of dyes are specified in the examples.  Reference has been directed by the Comptroller to Specification 878,362.ALSO:Light-sensitive materials are protected against the injurious effects of light by coating them with compositions containing at least one compound of the general formula <FORM:0991142/B1-B2/1> wherein R1 represents hydrogen or an alkyl, alkenyl, cycloalkyl or aralkyl radical which are possibly substituted by carboxyl or carboxylic acid ester groups and R1 and "Acyl", together with the amino-nitrogen atom, can form a ring when R1 is a carbonyl or unsubstituted or alkyl-substituted methylene group, and wherein the nucleus may be substituted at the 4, 5 or 6 positions by alkyl, alkoxy, carboxy, carboxylic acid ester or amide, sulphonic acid amide and alkylsulphonyl groups or halogen and at the 41 and 51 positions by alkyl, cyclo-alkyl, aralkyl and aryl groups, alkoxy groups or halogens. The "Acyl" group is a radical of the formula <FORM:0991142/B1-B2/2> wherein X is a carbon atom or the radical <FORM:0991142/B1-B2/3> and Y is oxygen, an imino group which with X and R2 forms a s-triazine or pyrimidine ring or, when X is carbon, a sulphur atom, and R2 is an alkenyl, cycloalkyl, aralkyl or substituted or unsubstituted alkyl or aryl group or, if X is carbon, R2 is hydrogen or an alkenyloxy, cycloalkyloxy or substituted or unsubstituted alkoxy, aryloxy or aralkyloxy group, or a substituted or unsubstituted amino group, an imino group of a saturated monocyclic heterocycle or if R1 and R2 are linked together, together with X and R1, R2 represents the remainder of a lactam or dioxopyrrolidine ring.  Specific mention is made of coating glass sheets.  Reference has been directed by the Comptroller to Specification 878,362.